硫铁化物/红壤基沸石复合材料在 Cr(VI) 污染地下水修复中的应用

地下水重金属污染严重威胁人类饮用水安全，受到人们的广泛关注。Cr(VI)因其高毒性、易迁移和难治理等特性，已成为地下水中重金属污染的重要议题之一。对于Cr(VI)污染水体的修复，传统的方法是先将Cr(VI)化学还原为Cr(III)，再添加其它试剂将Cr(III)固定。这种先还原后固定的方式会使得Cr(VI)的修复过程复杂化，造成多余的能源和试剂消耗，并有可能引发严重的二次污染。因此，开发既能还原Cr(VI)又能同时将还原后的Cr(III)固定的双功能材料，对Cr(VI)污染地下水的修复有重要意义。

本研究从Cr(VI)污染地下水修复角度出发，旨在同时实现Cr(VI)的还原以及Cr(III)的固定。以我国南方地区广泛分布的红壤为原料，采用水热法合成红壤基ANA型沸石分子筛（Re-ANA）。然后以该具有优良阳离子交换性能的ANA型沸石为基底材料，以具有化学还原性能和潜在光还原性能的硫铁化物为改性物质，分别采用水热法和溶剂热法开发了FeS₂/Re-ANA（PM/RA）和Fe₃S₄/Re-ANA（GRA）两种复合材料用于Cr(VI)污染地下水的修复。得到主要结果如下：

（1）在初始浓度为1 mg/L、pH值为6的Cr(VI)溶液中，PM/RA-3 对Cr(VI)的去除率达到98.90%，Cr(VI)残留浓度为0.011 mg/L，达到GB/T 14848-2017《地下水质量标准》第III类标准，也满足世界卫生组织规定的饮用水质量控制准则。整个去除过程中，Cr(III)的浓度始终维持在0.05 mg/L以下，同时实现了Cr(VI)的还原以及Cr(III)的固定。环境因素影响研究表明，较高的PM/RA-3投加剂量、较低的初始Cr(VI)浓度、较低的初始溶液pH值有助于Cr(VI)的去除。机理研究表明，PM/RA-3中的FeS₂，既能作为还原剂实现对Cr(VI)的化学还原，也能作为光催化剂实现对部分Cr(VI)的光还原。还原后的Cr(III)与Re-ANA孔道中的Na⁺发生离子交换并固定在其中，或被吸附在PM/RA-3的表面。固定床柱吸附实验研究表明，PM/RA-3填充量为1 g、进水流速为1 mL/min时，可使70 mL左右的实际Cr(VI)污染地下水达到标准排放，该材料有望在可渗透反应墙等实际应用场景中修复Cr(VI)污染地下水。Thomas、Yoon-Nelson和Adams-Bohart模型均能很好地描述固定床柱吸附实验研究中PM/RA-3处理Cr(VI)污染地下水的过程，Thomas模型预测PM/RA-3对Cr(VI)的最大去除容量为146.210 mg/kg，Yoon-Nelson模型的拟合结果得出获得50%穿透率的时间为150.267 min，Adams-Bohart模型的拟合结果得出单位柱体积去除Cr(VI)的容量为93.080 mg/L，表面扩散是Cr(VI)去除过程中的限速步骤。

（2）在初始浓度为1 mg/L、pH值为6的Cr(VI)溶液中，GRA-3对Cr(VI) 的去除率达到99.40%，Cr(VI)残留浓度为0.006 mg/L，达到GB/T 14848-2017《地下水质量标准》第III类标准，也满足世界卫生组织规定的饮用水质量控制准则。整个去除过程中，Cr(III)的浓度始终维持在0.01 mg/L以下，同时 实现了Cr(VI)的还 原以及Cr(III)的固定。环境因素影响研究表明，较高的GRA-3投加剂量、较低的初始Cr(VI)浓度、较低的初始溶液pH值有助于Cr(VI)的去除。机理研究表明，GRA-3中的Fe₃S₄，既能作为还原剂实现对Cr(VI)的化学还原，也能作为光催化剂实现对部分Cr(VI)的光还原。还原后的Cr(III)阳离子与Re-ANA孔道中的Na⁺发生离子交换并固定在其中，或被吸附在GRA-3的表面。固定床柱吸附实验研究表明，GRA-3填充量为0.2 g、进水流速为1 mL/min时，可使100 mL左右的实际Cr(VI)污染地下水达到标准排放，该材料有望在可渗透反应墙等实际应用场景中修复Cr(VI)污染地下水。Yan模型能很好地描述固定床柱吸附实验研究中GRA-3处理Cr(VI)污染地下水的过程，表明该过程中存在多个限速步骤，如固体表面的扩散和传质等。

The severe contamination of groundwater by heavy metals poses a significant threat to the safety of drinking water for humans. Due to its high toxicity, facile migration, and resistance to degradation, Cr(VI) has emerged as a critical issue in groundwater pollution. Traditional methods for remediating Cr(VI)-contaminated water involve chemically reducing Cr(VI) to Cr(III) followed by the addition of absorbents to immobilize the reduced Cr(III) products. With the traditional reduction combined with post-immobilization methods, the further Cr(III) immobilization will complicate the processes of Cr(VI) remediation and lead to excessive energy and reagent consumption along with potential secondary pollution. Therefore, it is of paramount importance to develop bifunctional materials to simultaneously reduce Cr(VI) and immobilize the reduced Cr(III) for the Cr(VI)-contaminated groundwater remediation.

This study focuses on the Cr(VI)-contaminated groundwater remediation, aiming to achieve simultaneous Cr(VI) reduction and Cr(III) immobilization. Utilizing red soil widely distributed in southern China as the raw material, red soil-based ANA-type zeolite (Re-ANA) was synthesized via a hydrothermal method. Subsequently, benefiting from the excellent cation exchange properties within ANA-type zeolite and the chemical reduction and potential photoreduction capabilities within iron sulfide, FeS₂/Re-ANA (PM/RA) and Fe₃S₄/Re-ANA (GRA) composite materials were developed for the remediation of Cr(VI)-contaminated groundwater via hydrothermal and solvothermal methods, respectively. The main outcomes are summarized as follows:

(1) In a Cr(VI) solution with an initial concentration of 1 mg/L and pH of 6, PM/RA-3 achieved a removal efficiency of 98.90% for Cr(VI), resulting in a residual concentration of 0.011 mg/L, meeting the Class III standard of GB/T 14848-2017 for groundwater quality and satisfying the drinking water quality control criteria specified by WHO. During the whole removal process, the concentration of Cr(III) was less than 0.05 mg/L, indicating the Cr(III) immobilization along with the Cr(VI) reduction. Environmental factor studies indicated that a higher dosage of PM/RA-3, lower initial Cr(VI) concentration, and lower initial solution pH value contributed to the Cr(VI) removal. Mechanistic studies revealed that Cr(VI) was partially chemically reduced and partially photoreduced by FeS₂ in PM/RA-3, acting as a reducing agent and a photocatalyst, respectively. The as-reduced Cr(III) was either ion-exchanged with Na⁺ in the pores of Re-ANA and immobilized therein or adsorbed on the surface of PM/RA-3. Fixed-bed column adsorption experiments illustrated that approximately 70 mL of actual Cr(VI)-contaminated groundwater could meet the discharge standards, with the PM/RA-3 filling amount of 1 g and the inlet flow rate of 1 mL/min, indicating the material's potential for Cr(VI)-contaminated groundwater remediation in practical applications such as permeable reactive barriers. The Thomas, Yoon-Nelson, and Adams-Bohart models adequately described the treatment process, with the Thomas model predicting a maximum removal capacity of 146.210 mg/kg for Cr(VI), the Yoon-Nelson model yielding a time of 150.267 min to achieve 50% breakthrough, and the Adams-Bohart model indicating a capacity of 93.080 mg/L for the removal of Cr(VI) per unit column volume, with surface diffusion being the limiting step in the Cr(VI) removal process.

(2) In a Cr(VI) solution with an initial concentration of 1 mg/L and pH of 6, GRA-3 achieved a removal efficiency of 99.40% for Cr(VI), resulting in a residual concentration of 0.006 mg/L, meeting the Class III standard of GB/T 14848-2017 for groundwater quality and satisfying the drinking water quality control criteria specified by WHO. During the whole removal process, the concentration of Cr(III) was below 0.01 mg/L, indicating the Cr(III) immobilization along with the Cr(VI) reduction.  Environmental factor studies indicated that a higher dosage of GRA-3, lower initial Cr(VI) concentration, and lower initial solution pH value contributed to the Cr(VI) removal. Mechanistic studies revealed that Cr(VI) was partially chemically reduced and partially photoreduced by Fe₃S₄ in GRA-3, serving as a reducing agent and a photocatalyst, respectively. The as-reduced Cr(III) was either ion-exchanged with Na⁺ in the pores of Re-ANA and immobilized therein or adsorbed on the surface of GRA-3. Fixed-bed column adsorption experiments demonstrated that approximately 100 mL of actual Cr(VI)-contaminated groundwater could meet the discharge standards, with the GRA-3 filling amount of 0.2 g and the inlet flow rate of 1 mL/min, indicating the material's potential for Cr(VI)-contaminated groundwater remediation in practical applications such as permeable reactive barriers. The Yan model adequately described the treatment process, indicating the existence of multiple limiting steps in the process, such as surface diffusion and mass transfer.

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